Dimethyl Sulfoxide → HCID 25139404, compound

HRID 2272810Notes

Reaction equation

HRID 2272810 reaction equation
CO[C:3]1[CH:10]=[CH:9][C:6]([CH2:7]N)=[CH:5][CH:4]=1.O[C@@H]1[C@H](O)[C@@H](OC)C(C)(C)O[C@H]1OC1C(C)=C2C([CH:28]=[C:29]([NH:36][C:37]([C:39]3[CH:40]=[C:41](C4C=CC=C(C)C=4)[C:42]([O:45][CH3:46])=[CH:43][CH:44]=3)=O)[C:30](=O)O2)=CC=1.[O-]P([O-])([O-])=O.[K+].[K+].[K+].[NH:62]1[CH2:69][CH2:68][CH2:67][C@H:63]1[C:64](O)=[O:65].[CH3:70]S(C)=O>>[CH3:46][O:45][C:42]1[CH:41]=[CH:40][C:39]([CH2:37][NH:36][C:29]2[CH:30]=[N:62][C:69]3[C:68]([CH:28]=2)=[CH:67][CH:63]=[C:64]([O:65][CH2:7][C:6]2[CH:9]=[CH:10][CH:3]=[CH:4][CH:5]=2)[CH:70]=3)=[CH:44][CH:43]=1

Participants

6

Reactant 5

HCID 679Dimethyl SulfoxideHCID 62657Potassium Phosphate, TribasicHCID 754524-MethoxybenzylamineHCID 145742L-ProlineHCID 24851280HCID 24851280, compound

Product 1

HCID 25139404HCID 25139404, compoundYield 73%

Conditions

Temperature
80 °C

Procedure

4-Methoxy-benzylamine (1.77 mL, 1.87 g, 13.64 mmol) and anhydrous DMSO (2.90 mL) were added to a high-pressure flask charged with 30 (1.65 g, 5.26 mmol), K3PO4 (2.36 g, 11.10 mmol), CuII (167 mg, 0.88 mmol), and L-(−)-proline (141 mg, 1.22 mmol); the sealed flask was heated to 80° C. for 44 hours. After cooling to room temperature, reaction contents were partitioned between water (50 mL) and EtOAc (100 mL), then were extracted with EtOAc (2×100 mL). The combined organic layers were washed with saturated aqueous NaCl solution (200 mL), dried (Na2SO4), filtered, and concentrated. The residue was purified via column chromatography (SiO2, 1:1 Hexanes:EtOAc) to give 31 as a light yellow amorphous solid (1.43 g, 73%): 1H NMR (CDCl3, 500 MHz) δ 8.44 (d, J=2.8 Hz, 1H), 7.52 (d, J=8.9 Hz, 1H), 7.50 (m, 2H), 7.43-7.38 (m, 3H), 7.36-7.32 (m, 3H), 7.20 (dd, J=8.9, 2.6 Hz, 1H), 7.06 (d, J=2.7 Hz, 1H), 6.91 (m, 2H), 5.17 (s, 2H), 4.35 (d, J=4.8 Hz, 2H), 4.17 (bt, J=4.8 Hz, 1H), 3.82 (s, 3H); 13C NMR (CDCl3, 125 MHz) δ 159.3, 156.9, 143.4, 143.3, 140.5, 137.0, 130.6, 129.1 (2C), 128.8 (2C), 128.2, 127.9 (2C), 127.3, 124.7, 120.4, 114.4 (2C), 112.0, 109.0, 70.3, 55.5, 48.0; IR (film) νmax 3279, 2953, 2833, 1609, 1510, 1377, 1354, 1302, 1225, 1175, 1124, 1028, 995, 868, 818, 762, 708 cm−1; HRMS (ESI+) m/z: [M+H]+ calcd for C24H22N2O2, 371.1759. found, 371.1732.

Workup

  1. temperatureAfter cooling to room temperature
  2. customreaction contents
  3. customwere partitioned between water (50 mL) and EtOAc (100 mL)
  4. extractionwere extracted with EtOAc (2×100 mL)
  5. washThe combined organic layers were washed with saturated aqueous NaCl solution (200 mL)
  6. dry with materialdried (Na2SO4)
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was purified via column chromatography (SiO2, 1:1 Hexanes:EtOAc)

Sources & evidence

ORD record
ord-0ed552622163460fa525354b3c27a701
Source dataset
uspto-grants-2015_09
Patent number
US09120774B2

Reaction notes

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